JP6585605B2 - 有機化合物における、またはそれに関する改善 - Google Patents
有機化合物における、またはそれに関する改善 Download PDFInfo
- Publication number
- JP6585605B2 JP6585605B2 JP2016549636A JP2016549636A JP6585605B2 JP 6585605 B2 JP6585605 B2 JP 6585605B2 JP 2016549636 A JP2016549636 A JP 2016549636A JP 2016549636 A JP2016549636 A JP 2016549636A JP 6585605 B2 JP6585605 B2 JP 6585605B2
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- nitroso
- carbon
- mnu
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/02—Addition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/08—Isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
- C07C49/553—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/50—Spiro compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
I)二相混合物中でのMNCの発生、
II)有機MNC含有液相の水相からの分離および
III)有機MNC含有液相をアルケン基質、水性塩基および触媒を含む混合物中に移送し、それによってアルケン基質をシクロプロパン化すること
を含む、前記方法を提供する。
無極性GC/MS:50℃/2分、20℃/分 200℃、35℃/分 270℃。HP 7890A Series GCシステムを有するGC/MS Agilent 5975C MSD。無極性カラム:SGEからのBPX5、5%フェニル95%ジメチルポリシロキサン0.22mm×0.25mm×12m。キャリアガス:ヘリウム。注射器温度:230℃。分割1:50。流量:1.0ml/分。移送ライン:250℃。MS−四重極:106℃。MS源:230℃。
トルエン(1ml)中のPd(acac)2(5.6mg、0.05%)を、0〜5℃で、ミルセン85% tech.(5g、31mmol)のトルエン(25ml)および40%KOH水溶液(15ml)中の撹拌した混合物に加える。トルエン中のN−ニトロソ−ジメチルウレタン 1.8M(30ml、55mmol、例2から)を、0〜5℃で1時間にわたって加える。強度に黄色の反応混合物は、GCによるΔ−ミルセン(77%)およびΔ2−ミルセン(7%)への、0〜5℃での1時間後の87%の変換および室温での18時間後の96%の変換を示す。有機相を分離し、水相をトルエン(50ml)で抽出する。両方の有機相を、酢酸(25ml)、水(25ml)、10%NaOH(25ml)および水(3×25ml)で洗浄する。有機相を合わせ、MgSO4で乾燥し、ろ過し、減圧下で濃縮する。残りの黄色油(4.2g)を、100〜120℃/20mbarでバルブ・ツー・バルブ(bulb-to-bulb)蒸留し、2%のミルセン、84%のΔ−ミルセン1および8%のΔ2−ミルセン2を含む2.9g(61%)の生成物混合物を得る。これらの構成成分の分析的なデータは、例4において得られたものと同一である。
Pd(acac)2(21mg、0.5%)を、0〜5℃で、新たに蒸留したミルセン(2g、15mmol)および40%KOH水溶液(5ml)の撹拌した混合物に加える。WO 2013110932に記載されているように製造したNMK(4.6g、29mmol)を、0〜5℃で0.5時間以内に滴加する。0〜5℃でさらに1時間後、茶色懸濁液を、25℃でさらに2時間撹拌する(GCにより87%変換)。21時間後、混合物を酢酸(10ml)で反応停止し、二相混合物をtert−ブチルメチルエーテル(2×50ml)で抽出する。有機層を、水(25ml)、10%NaOH(25ml)および水(25ml)で洗浄する。両方の有機相を合わせ、MgSO4で乾燥し、ろ過し、減圧下で濃縮する。残りの黄色油(4.1g)を、50〜150℃/10mbarでバルブ・ツー・バルブ蒸留し、1gのメシチルオキシド(35%)、0.26gのミルセン(14%)、1.4gのΔ−ミルセン1(69%)および0.07gのΔ2−ミルセン2(3%)を得る。主要な構成成分の分析的データは、例4において得られたものと同一である。
例9に記載したのと同様の条件の下で、E−β−ファルネセン(193.4g、0.945mol)を、MNU(1.3mol)を有するジクロロメタン(40ml)および40%KOH(400ml)にあらかじめ溶解したPd(acac)2(0.58g、1.9mmol、0.2%)の存在下で、800mlのNMP中でシクロプロパン化する(MNU/NMP滴下漏斗中でわずかであるが一定のガス発生の下で)。後処理によって、3%のE−β−ファルネセン、75%のモノシクロプロパン4および12%のビスシクロプロパン5を含む、わずかに黄色の液体(202g)が得られる。1gのK2CO3(1g)の添加および40〜60mbarでの30cmの鋼コイルカラムでの蒸留によって、6.3gのE−β−ファルネセン(3% corr)が125〜135℃で、147gのモノシクロプロパン4(68% corr)が135〜145℃で、20.3gのビスシクロプロパン5(10% corr)が145〜155℃で、および18gの残留物が得られる。画分をプールして、100%純度の92gのモノシクロプロパン4および93%純度の10gのビスシクロプロパン5を無色液体として得る。
1H-NMR (CDCl3, 400 MHz): 5.1 (2 m, 2 H), 4.6 (2 H), 2.2 (2 H), 2.1 (4 H), 2.0 (2 H), 1.7 (s, 3 H), 1.6 (2 s, 6 H), 1.3 (1 H), 0.6 (2 H), 0.45 (2 H) ppm. 13C-NMR (CDCl3, 400 MHz): 150.9 (s), 135.1 (s), 131.2 (s), 124.4 (d), 124.1 (d), 106.0 (t), 39.7 (t), 35.9 (t), 26.7 (t), 25.7 (q), 17.7 (q), 16.0 (d), 6.0 (t) ppm. GC/MS: 218 (2%, M+), 203 (5%, [M - 15]+), 175 (11%), 147 (31%), 134 (15%), 133 (20%), 121 (12%), 107 (55%), 95 (16%), 93 (30%), 91 (20%), 82 (11%), 81 (33%), 79 (42%), 69 (100%), 67 (22%), 55 (20%), 53 (21%), 41 (75%). IR (film): 3081 (w), 2967 (m), 2915 (m), 2854 (m), 1642 (m), 1439 (m), 1377 (m), 1107 (w), 1047 (w), 1018 (m), 875 (s), 819 (m), 629 (w). Anal. calcd. for C16H26: C, 88.00; H, 12.00. Found: C, 87.80; H, 12.01.
1H-NMR (CDCl3, 400 MHz): 5.15 (2 m, 2 H), 2.25 (m, 2 H), 2.05 (m, 2 H), 2.0 (m, 2 H), 1.7 (s, 3 H), 1.65 (2 s, 6 H), 1.4 (m, 2 H), 1.05 (m, 1 H), 0.3 (m, 2 H), 0.15 (4 H), -0.05 (m, 2 H) ppm. 13C-NMR (CDCl3, 400 MHz): 134.5 (s), 131.2 (s), 124.9 (d), 124.4 (d), 40.0 (t), 39.7 (t), 26.7 (t), 25.7 (q), 25.5 (t), 20.3 (s), 17.6 (q), 15.9 (q), 14.3 (d), 9.2 (2 C, t), 1.9 (2 C, t) ppm. GC/MS: 232 (0.2%, M+), 217 (3%, [M - 15]+), 204 (4%), 189 (10%), 161 (8%), 147 (12%), 121 (22%), 107 (20%), 95 (27%), 93 (31%), 91 (13%), 81 (42%), 79 (30%), 69 (100%), 67 (33%), 55 (24%), 53 (16%), 41 (67%). IR (film): 3075 (w), 3001 (w), 2967 (m), 2913 (m), 2849 (m), 1669 (w), 1448 (m), 1377 (m), 1107 (m), 1045 (m), 1011 (s), 984 (w), 952 (w), 884 (w), 819 (m), 740 (w), 664 (w). Anal. calcd. for C17H28: C, 87.86; H, 12.14. Found: C, 87.59; H, 12.09.
Toscanol16のGCMS:162 (22%, M+), 147 (8%), 134 (23%), 121 (100%), 119 (11%), 91 (18%), 78 (8%), 77 (10%), 65 (7%).
Claims (18)
- 炭素−炭素二重結合をシクロプロパン環に変換する方法であって、当該方法が、N−アルキル−N−ニトロソ化合物を炭素−炭素二重結合を保有する基質と反応させる、ここでN−アルキル−N−ニトロソ化合物がin situで発生し、N−アルキル−N−ニトロソ化合物を最初に単離せずに基質に加える、ステップを含む、前記方法。
- N−アルキル−N−ニトロソ化合物がN−アルキル−N−ニトロソ尿素の有機溶液である、請求項1に記載の方法。
- N−アルキル−N−ニトロソ化合物がN−メチル−N−ニトロソ化合物(MNC)である、請求項1に記載の方法。
- N−アルキル−N−ニトロソ化合物がN−メチル−N−ニトロソ−尿素(MNU)、N−メチル−N−ニトロソ−p−トルエンスルホンアミド(DiazaldTM)、N−ニトロソ−ジメチルウレタン、ニトロソ−EMUおよびN−ニトロソ−β−メチルアミノイソブチルメチルケトン(NMK)からなる群から選択される、請求項1に記載の方法。
- N−アルキル−N−ニトロソ化合物を炭素−炭素二重結合を保有する基質と、水性塩基および触媒の存在下で反応させる、請求項1〜4のいずれか一項に記載の方法。
- 炭素−炭素二重結合をシクロプロパン環に変換する方法であって、以下のステップ:
I)液相中でのN−アルキル−N−ニトロソ化合物の合成、
II)N−アルキル−N−ニトロソ化合物含有有機液相の水相からの分離、および
III)有機液相中のN−アルキル−N−ニトロソ化合物を、アルケン基質を含む混合物中に移送し、それによってアルケン基質をシクロプロパン化すること
を含む、前記方法。 - 触媒が遷移金属触媒である、請求項5に記載の方法。
- 遷移金属触媒が、パラジウム触媒である、請求項7に記載の方法。
- パラジウム触媒が、Pd(acac)2、Pd(OAc)2またはPdCl2である、請求項8に記載の方法。
- 炭素−炭素二重結合を保有する基質が末端(単置換)アルケンである、請求項1〜5および7〜9のいずれか一項に記載の方法。
- 炭素−炭素二重結合を保有する基質が式
ならびにR3は、アルキル、アルキリデンまたはアリールであり、それは分枝状または非分枝状および置換または非置換であってもよい、
で表される化合物である、請求項1〜5および7〜10のいずれか一項に記載の方法。 - 基質がイソプレノイドである、請求項10または11に記載の方法。
- 末端イソプレン単位にて>70%の選択性でモノ−またはビス−シクロプロパン化されている、ミルセン、オシメン、ファルネセンまたは高級ポリプレノイド誘導体を生じる、請求項1〜12のいずれか一項に記載の方法。
- 末端イソプレン単位にて>80%の選択性でモノ−またはビス−シクロプロパン化されている、ミルセン、オシメン、ファルネセンまたは高級ポリプレノイド誘導体を生じる、請求項1〜13のいずれか一項に記載の方法。
- 末端イソプレン単位にて>90%の選択性でモノ−またはビス−シクロプロパン化されている、ミルセン、オシメン、ファルネセンまたは高級ポリプレノイド誘導体を生じる、請求項1〜14のいずれか一項に記載の方法。
- 式
で表される化合物を生じる、請求項1〜15のいずれか一項に記載の方法。 - 式
ならびにR’’は、任意に置換されているC3〜C10ラジカルである、
で表される化合物を生じる、請求項1〜16のいずれか一項に記載の方法。 - 任意に置換されているC3〜C10ラジカルが、1個または2個以上のヘテロ原子、イミン、アルコール、アセタール、または、エステル、アルデヒドもしくはケトンを含むカルボニル基を含み、不飽和である、請求項17に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB1318886.7A GB201318886D0 (en) | 2013-10-25 | 2013-10-25 | Improvements i or relating to organic compounds |
GB1318886.7 | 2013-10-25 | ||
PCT/EP2014/072882 WO2015059290A1 (en) | 2013-10-25 | 2014-10-24 | Improvements in or relating to organic compounds |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2016538335A JP2016538335A (ja) | 2016-12-08 |
JP2016538335A5 JP2016538335A5 (ja) | 2017-11-30 |
JP6585605B2 true JP6585605B2 (ja) | 2019-10-02 |
Family
ID=49767164
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016549636A Active JP6585605B2 (ja) | 2013-10-25 | 2014-10-24 | 有機化合物における、またはそれに関する改善 |
Country Status (10)
Country | Link |
---|---|
US (2) | US9718741B2 (ja) |
EP (1) | EP3060535B1 (ja) |
JP (1) | JP6585605B2 (ja) |
CN (1) | CN105658604B (ja) |
ES (1) | ES2822673T3 (ja) |
GB (1) | GB201318886D0 (ja) |
IL (1) | IL244929B (ja) |
MX (1) | MX2016005053A (ja) |
SG (1) | SG11201602725UA (ja) |
WO (1) | WO2015059290A1 (ja) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB201507170D0 (en) | 2015-04-24 | 2015-06-10 | Givaudan Sa | Process |
GB201507207D0 (en) | 2015-04-24 | 2015-06-10 | Givaudan Sa | Enzymes and applications thereof |
GB201516396D0 (en) | 2015-09-16 | 2015-10-28 | Givaudan Sa | Improvements in or relating to organic compounds |
GB201618090D0 (en) | 2016-10-26 | 2016-12-07 | Givaudan Sa | Product |
GB201720211D0 (en) * | 2017-12-05 | 2018-01-17 | Givaudan Sa | Improvements in or relating to organic compounds |
CN108484347B (zh) * | 2018-04-28 | 2021-02-05 | 江苏八巨药业有限公司 | 一种末端异戊二烯类化合物环丙烷化的制备方法 |
GB201810514D0 (en) * | 2018-06-27 | 2018-08-15 | Givaudan Sa | Improvements in or relating to organic compounds |
CN110577484A (zh) * | 2019-07-02 | 2019-12-17 | 凯莱英医药集团(天津)股份有限公司 | 环丙烷类化合物连续合成的方法及装置 |
JP7441863B2 (ja) * | 2019-07-02 | 2024-03-01 | アシムケム ラボラトリーズ (ティエンジン) カンパニー リミテッド | シクロプロパン系化合物の連続合成方法及び装置 |
CN111517991A (zh) * | 2020-04-24 | 2020-08-11 | 常州齐晖药业有限公司 | 一种地克珠利杂质a的制备方法 |
CN111574411A (zh) * | 2020-04-24 | 2020-08-25 | 常州齐晖药业有限公司 | 一种地克珠利杂质b的制备方法 |
CN113480404A (zh) * | 2021-06-30 | 2021-10-08 | 中昊(大连)化工研究设计院有限公司 | 一种环丙基溴合成的新方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4650881A (en) | 1985-04-01 | 1987-03-17 | Iowa State University Research Foundation, Inc. | Synthesis of isocoumarins via thallation-olefination of arenes |
JPS62129240A (ja) * | 1985-11-29 | 1987-06-11 | Tokyo Tanabe Co Ltd | 4′−シクロプロピルフエノン誘導体 |
DE4327748B4 (de) * | 1993-08-18 | 2006-07-20 | Merck Patent Gmbh | Cyclopropyl- und Cyclobutyl-Derivate |
JP3385264B2 (ja) * | 1995-04-11 | 2003-03-10 | 三井化学株式会社 | 置換チオフェン誘導体およびこれを有効成分とする農園芸用殺菌剤 |
ATE201016T1 (de) * | 1995-06-09 | 2001-05-15 | Hoffmann La Roche | Pyrimidindion-, pyrimidintrion-, triazindion- derivate als alpha-1-adrenergische rezeptorantagonisten |
US5854405A (en) | 1997-11-13 | 1998-12-29 | Aerojet-General Corporation | Continuous process for diazomethane from an n-methyl-n-nitrosoamine and from methylurea through n-methyl-n-nitrosourea |
FR2801051B1 (fr) * | 1999-11-17 | 2001-12-14 | Adir | Nouveaux composes aminopyrroline, leur procede de preparation et les compositions pharmaceutiques qui les contiennent |
BRPI0507944A (pt) * | 2004-02-24 | 2007-07-24 | Sankyo Co | composição farmacêutica |
WO2007071766A2 (en) * | 2005-12-22 | 2007-06-28 | Transtech Pharma | Phenoxy acetic acids as ppar delta activators |
WO2010131145A1 (en) | 2009-05-12 | 2010-11-18 | Pfizer Limited | Cyclobutenedione derivatives |
PT2635548E (pt) * | 2010-11-01 | 2015-03-24 | Dpx Fine Chemicals Austria Gmbh & Co Kg | Produção e reação contínuas de um composto diazo |
US8722916B2 (en) * | 2010-12-01 | 2014-05-13 | Rigel Pharmaceuticals, Inc. | Cyclopropyl MIDA boronate |
JP2014088326A (ja) * | 2011-02-22 | 2014-05-15 | Astellas Pharma Inc | ポリペプチド化合物 |
US20120226041A1 (en) * | 2011-03-04 | 2012-09-06 | The Board Of Trustees Of The University Of Illinois | Catalysts and boronate esters |
US9073924B2 (en) * | 2011-09-13 | 2015-07-07 | Glaxosmithkline Llc | Azaindazoles |
-
2013
- 2013-10-25 GB GBGB1318886.7A patent/GB201318886D0/en not_active Ceased
-
2014
- 2014-10-24 EP EP14787207.1A patent/EP3060535B1/en active Active
- 2014-10-24 WO PCT/EP2014/072882 patent/WO2015059290A1/en active Application Filing
- 2014-10-24 JP JP2016549636A patent/JP6585605B2/ja active Active
- 2014-10-24 MX MX2016005053A patent/MX2016005053A/es unknown
- 2014-10-24 SG SG11201602725UA patent/SG11201602725UA/en unknown
- 2014-10-24 US US15/031,158 patent/US9718741B2/en active Active
- 2014-10-24 ES ES14787207T patent/ES2822673T3/es active Active
- 2014-10-24 CN CN201480058480.5A patent/CN105658604B/zh active Active
-
2016
- 2016-04-05 IL IL244929A patent/IL244929B/en active IP Right Grant
-
2017
- 2017-06-22 US US15/630,060 patent/US20170283342A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US9718741B2 (en) | 2017-08-01 |
CN105658604A (zh) | 2016-06-08 |
EP3060535A1 (en) | 2016-08-31 |
WO2015059290A1 (en) | 2015-04-30 |
US20160280615A1 (en) | 2016-09-29 |
IL244929B (en) | 2019-06-30 |
IL244929A0 (en) | 2016-05-31 |
EP3060535B1 (en) | 2020-08-05 |
JP2016538335A (ja) | 2016-12-08 |
MX2016005053A (es) | 2016-08-17 |
US20170283342A1 (en) | 2017-10-05 |
SG11201602725UA (en) | 2016-05-30 |
CN105658604B (zh) | 2019-10-25 |
GB201318886D0 (en) | 2013-12-11 |
ES2822673T3 (es) | 2021-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6585605B2 (ja) | 有機化合物における、またはそれに関する改善 | |
JP7330226B2 (ja) | N-メチル-n-ニトロソ化合物を使用したオレフィンのシクロプロパン化のためのプロセス | |
JP6929328B2 (ja) | 高沸点アルデヒド生成物の分離及び触媒回収のための抽出プロセス | |
JP6101636B2 (ja) | バナジウム錯体を用いたファルネサールの製造方法 | |
US20130345445A1 (en) | Reduction of c-0 bonds by catalytic transfer hydrogenolysis | |
MX2014012447A (es) | Proceso para la reduccion quimoselectiva de esteres carboxilicos terminalmente saturados. | |
Ganchegui et al. | Palladium-catalyzed isomerization of (homo-) allylic alcohols in molten tetrabutylammonium bromide, a recyclable system | |
Zhang et al. | Indium (III) mediated Markovnikov addition of malonates and β-ketoesters to terminal alkynes and the formation of Knoevenagel condensation products | |
EP2953920A1 (en) | Process for the isomerisation of an exo double bond | |
Bandarenko et al. | Synthesis of raspberry and ginger ketones by nickel boride-catalyzed hydrogenation of 4-arylbut-3-en-2-ones | |
FR3013046A1 (fr) | Procede de synthese d'esters et catalyseur de ladite synthese | |
JPH0741451A (ja) | テルペン系ケトン類の製造方法 | |
Yang et al. | Asymmetric synthesis of 3-hydroxyl-2-alkanones via tandem organocatalytic aminoxylation of aldehydes and chemoselective diazomethane homologation | |
BR112016008531B1 (pt) | Aperfeiçoamentos em ou relacionados a compostos orgânicos | |
Sivcev et al. | Unique shortening of carbon chain during reduction of aliphatic nitro compounds to amines in the presence of supercritical isopropanol on alumina | |
US6118027A (en) | Preparation of unsaturated aldehydes from propargyl alcohol and conjugated diolefins | |
Lim et al. | Aerobic Oxidation of Benzylic Alcohols with Nitric Acid/Copper Bromide (II) in Ionic Liquid | |
Wol’f et al. | Effect of solvent nature on the catalytic hydroformylation of 2, 3-dihydrofuran | |
JP2019127453A (ja) | 第一級アミンの製造方法 | |
JP2016124788A (ja) | 長鎖ケトアルコールの製造方法およびそれを還元してなる長鎖ジオール | |
RU2528049C2 (ru) | Способ получения циклогексилалкилкетонов | |
Fujita et al. | Impact of Carbon Dioxide Pressurization on Catalytic Reactions | |
JP2003300946A (ja) | 光学活性3−アジドカルボン酸エステルの製造方法 | |
WO2000047590A1 (fr) | Tris [(1h,1h, 2h,2h-perfluoroalkyl) aryl]phosphites et leurs applications en catalyse | |
FR2862639A1 (fr) | Procede de c allylation de phenols |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171023 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171023 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180817 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180824 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181122 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190329 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190612 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190902 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190905 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6585605 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |